Quaternary fatty acid triethanolamine ester salts and their use as fabric softeners

ABSTRACT

The present invention relates to biodegradable softener compounds of the formula (1): [(R) 4-m —N( + )—[(CH 2 ) n —Y—R 1 ] m ]X( − ) with an acid value of no more than 6.5. A process for making said compound is also provided. The softener can be incorporated into softener compositions to form solid and liquid compositions, including liquid dispersions and clear compositions.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to fabric softening compounds andcomposition thereof useful for softening fabrics. It especially relatesto fabric softening compounds and/or compositions suitable forformulating textile softening compositions for use in the rinse cycle ofa textile laundering operation to provide excellentfabric-softening/static-control benefits, the compositions beingcharacterised by, e.g., reduced staining of fabric, excellent waterdispersibility, rewettability, and/or storage and viscosity stability atsub-normal temperatures, i.e., temperatures below normal roomtemperature, e.g., 25° C. The compositions of the invention arepreferably liquid softening compositions, and more preferably,translucent or clear liquid softening compositions.

BACKGROUND OF THE INVENTION

Clear softening compositions are known in the art. For example,EP-A-0,404,471 discloses clear softening compositions with at least 20%by weight softener and at least 5% by weight of a short chain organicacid.

Formulating softening compositions which are clear is however not theonly condition required of softening compositions. Indeed, suchcompositions are expected to provide an effective softening performanceon the treated fabric. In this respect, EP-A-0,550,361 disclosessoftening compounds with specific molar ratios of fatty acid fraction totertiary amine which provide effective softening performance withoutbeing detrimental to the fluidity and stability of compositioncontaining said compound.

It is now an object to provide a softening compound which provideseffective softening performance.

Still another object of the invention, is to provide a compositioncontaining said compound which are clear but still not detrimental tothe fluidity and stability of composition.

These objects have now surprisingly been met by producing the softeningcompound from the condensation of fatty acids with triethanolamine,wherein the condensation occurs for a period such that the condensationproduct has an acid value (AV) of less than 6.5, the condensationproduct subsequently being quaternized.

The AV of the compound is measured on the condensation product beforethe quaternisation step by the test method defined hereinafter.

For optimum softness benefit, it is preferred that the reactants arepresent in a molar ratio of fatty acid fraction to triethanolamine offrom 1:1 to 2.5:1.

The finding that a lower acid value of the invention compound leads tohigher softness performance when using the invention compound is verysurprising and unexpected. Indeed, as known from GB 2,039,556, theaddition of fatty acid provide an increase in the softness performanceof the softening composition. The Applicant, in this respect, has foundthat the addition of fatty acid, instead of decreasing the acid value,increased the acid value. Accordingly, it was generally believed thatthe softness performance in relation to the acid value followed a curveshowing a maximum at an AV above 10. To the contrary, it has been foundthat the softness performance followed a line whereby the higher theacid value, the less softening performance is obtained.

By effective softening performance, it is meant that the compound of thepresent invention provides better softening performance to fabricscompared to fabrics which have been treated with a similar compound butwith an AV above 6.5. In a preferred embodiment, the compound of theinvention provides better softness performance on treated fabricstherewith compared to compounds having the hereinbelow described molarratios but not the specified AV.

SUMMARY OF THE INVENTION

The present invention relates to a biodegradable fabric softenercompound comprising a quaternary ammonium salt, the quaternised ammoniumsalt being a quaternised product of condensation between:

a)-a fraction of saturated or unsaturated, linear or branched fattyacids, or of derivatives of said acids, said fatty acids or derivativeseach possessing a hydrocarbon chain in which the number of atoms isbetween 5 and 21, and

b)-triethanolamine, characterised in that said condensation product hasan acid value, measured by titration of the condensation product with astandard KOH solution against a phenolphtaleine indicator, of less than6.5.

In a preferred embodiment of the invention, the fatty acid fraction andthe triethanolamine are present in a molar ratio of from 1:1 to 2.5:1.

The present invention also relates to a process for making a softenercompound, and in particular said compound.

Also provided herein is a softening composition containing saidsoftening compound.

DETAILED DESCRIPTION OF THE INVENTION

I-Softener Compound

The essential component of the invention is a biodegradable fabricsoftener compound comprising a quaternary ammonium salt, the quaternisedammonium salt being a quaternised product of condensation between:

a)-a fraction of saturated or unsaturated, linear or branched fattyacids, or of derivatives of said acids, said fatty acids or derivativeseach possessing a hydrocarbon chain in which the number of atoms isbetween 5 and 21, and

b)-triethanolamine,

characterised in that said condensation product has an acid value,measured by titration of the condensation product with a standard KOHsolution against a phenolphtaleine indicator, of less than 6.5.

The acid value is preferably less than or equal to 5, more preferablyless than 3. Indeed, the lower the AV, the better softeness softnessperformance is obtained.

The acid value is determined by titration of the condensation productwith a standard KOH solution against a phenolphtaleine indicatoraccording to ISO#53402. The AV is expressed as mg KOH/g.

For optimum softness benefit, it is preferred that the reactants arepresent in a molar ratio of fatty acid fraction to triethanolamine offrom 1:1 to 2.5:1.

It has also been found that the optimum softness performance is alsoaffected by the detergent carry-over laundry conditions, and moreespecially by the presence of the anionic surfactant in the solution inwhich the softening composition is used. Indeed, the presence of anionicsurfactant that is usually carried over from the wash will interact withthe softener compound, thereby reducing its performance. Thus, dependingon usage conditions, the mole ratio of fatty acid/ triethanolamine canbe critical. Accordingly, where no rinse occurs between the wash cycleand the rinse cycle containing the softening compound, a high amount ofanionic surfactant will be carried over in the rinse cycle containingthe softening compound. In this instance, it has been found that a fattyacid fraction/triethanolamine mole ratio of 1.4:1 to 1.8:1 is preferred.By high amount of anionic surfactant, it is meant that the presence ofanionic in the rinse cycle at a level such that the molar ratio anionicsurfactant/cationic softener compound of the invention is at least 1/10.

Thus, according to another aspect of the invention, there is provided amethod of treating fabrics which comprises the step of contacting thefabrics in an aqueous medium containing the softener compound of theinvention or softening composition thereof wherein the fattyacid/triethanolamine mole ratio in the softener compound is from 1.4:1to 1.8:1, preferably 1.5:1 and the aqueous medium comprises a molarratio of anionic surfactant to said softener compound of the inventionof at least 1:10.

Where, on the other hand, an intermediate rinse cycle occurs between thewash and the later rinse cycle, less anionic surfactant, i.e. less than1:10 of a molar ratio anionic surfactant to cationic compound of theinvention, will then be carried over. Accordingly, it has been foundthat a fatty acid/triethanolamine mole ratio of 1.8:1 to 2.2:1 is thenpreferred. Accordingly, in another aspect of the invention, there isprovided a method of treating fabrics which comprises the step ofcontacting the fabrics in an aqueous medium containing the softenercompound of the invention or softening composition thereof wherein thefatty acid/triethanolamine mole ratio in the softener compound is from1.8:1 to 2:1, preferably 2.0:1 and the aqueous medium comprises a molarratio of anionic surfactant to said softener compound of the inventionof less than 1:10.

Preferred compounds of the invention include compounds having theformula:

wherein each R substituent is hydrogen or a short chain C₁-C₆ alkyl orhydroxyalkyl group; preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g.,methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like,benzyl, or mixtures thereof;

each m is in the range of 1 to 2.5;

each n is from 1 to 4; preferably 2;

each Y is —O—(O)C—, —(R)N—(O)C—, —C(O)—N(R)—, or —C(O)—O—; preferably—O—(O)C—; the sum of carbons in each R¹, plus one when Y is —O—(O)C— or—(R)N—(O)C— (“YR¹ sum”), is C₆-C₂₂, preferably C₁₂₋₂₂, more preferablyC₁₄-C₂₀, (hereinafter, R¹ and YR¹ are used interchangeably to representthe hydrophobic chain, the R¹ chain lengths in general being evennumbered for fatty alcohols and odd for fatty acids), but no more thanone R¹, or YR¹, sum being less than 12 and then the other R¹, or YR¹,sum is at least 16, with each R¹ comprising a long chain C₅-C₂₁ (orC₆-C₂₂), branched alkyl or unsaturated alkyl, preferably C₁₀-C₂₀ (orC₉-C₁₉) branched alkyl or unsaturated alkyl, most preferably C₁₂-C₁₈ (orC₁₁-C₁₇) branched alkyl, or unsaturated alkyl, optionally substituted,

For the unsaturated alkyl group, the Iodine Value of the parent fattyacid of this R¹ group is from 0 to 140, more preferably when used inclear softening composition the Iodine Value of the parent fatty acid ofthis R¹ group is from 50 to 130; whilst when used in dispersion theIodine Value of the parent fatty acid of this R¹ group is preferablyfrom 0 to 70 (As used herein, the “branched alkyl” groups include thosethat contain a substituent that is hydrophobic, even though they areattached to the main chain by bonds that are not carbon to carbon, e.g.,by oxygen, as in the alkoxy substituents, and the Iodine Value of a“parent” fatty acid, or “corresponding” fatty acid, is used to define alevel of unsaturation for an R¹ groups that is the same as the level ofunsaturation that would be present in a fatty acid containing the sameR¹ group. When an individual R¹ is both branched and unsaturated, it istreated as if it is branched.); and

wherein the counterion, X⁻, can be any softener-compatible anion;preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,and/or nitrate, more preferably methylsulfate.

Also suitable as softener compounds according to the invention are thosethat are prepared as a single compound from blends of all the differentbranched and unsaturated fatty acids that are represented (total fattyacid blend), rather than from blends of mixtures of separate finishedsoftener compound that are prepared from different portions of the totalfatty acid blend.

It is preferred that at least a substantial percentage of the fatty acylgroups are unsaturated, e.g., from 25% to 70%, preferably from 50% to65%. Polyunsaturated fatty acid groups can be used. The total level ofactive containing polyunsaturated fatty acyl groups (TPU) can be from 3%to 30%, preferably from 5% to 25%, more preferably from 10% to 18%. Bothcis and trans isomers can be used, preferably with a cis/trans ratio offrom 1:1 to 50:1, the minimum being 1:1, preferably at least 3:1, andmore preferably from 4:1 to 20:1. (As used herein, the “percent ofsoftener active” containing a given R¹ group is the same as thepercentage of that same R¹ group is to the total R¹ groups used to formall of the softener actives.)

The mixed branched-chain and unsaturated materials are easier toformulate than conventional saturated branched chain fabric softenercompounds. They can advantageously be used to form clear or translucentcompositions.

II-Process for Making Said Compound

Another essential feature of the invention is a process for making asoftener compound, in particular the softener compounds of theinvention. This include the steps of:

a)-reacting the fatty acid fraction comprising fatty acids of formulaR¹COOH in which R¹ is a long chain C₅-C₂₁ branched alkyl or unsaturatedalkyl, optionally substituted, with at least a triethanolamine, for aperiod such that the condensation product obtained compound has an acidvalue, measured by titration of the condensation product with a standardKOH solution against a phenolphtaleine indicator according to ISO#53402,of less than 6.5, and

b)-reacting the condensation product thereby obtained with an alkylatingagent, in the presence or absence of a solvent.

By fatty acid fraction, it is meant a mixture having fatty acids, fattyacid esters or mixtures therefore. This mixture can be eithercommercially available or provided by the reacting of a source oftriglycerides. By reacting, it is meant the process of:

(a) hydrogenating a triglyceride product comprising a mixture ofcompounds of the formula (1)

R¹—OCH₂—CHO(—R²)—CH₂O—R³  (1)

wherein R¹, R² and R³ are acyl groups of which at least 1% contain 16carbon atoms, and at least 70% contain 18 carbon atoms, provided thatsaid acyl groups containing 18 carbon atoms include predominantly monounsaturated acyl groups and minor amounts of saturated, diunsaturatedand triunsaturated acyl groups, under hydrogenation conditionswhereunder diunsaturated and triunsaturated acyl groups containing 18carbon atoms are hydrogenated provided that formation of saturated acylgroups containing 18 carbon atoms is minimized;

(b) hydrolyzing the hydrogenated product of step (a) to form glycerineand a mixture of fatty acids based on said acyl groups.

The triglyceride source is preferably derived from vegetable oils and/orpartially hydrogenated vegetable oils, such as, canola oil, saffloweroil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, ricebran oil, etc and mixtures of these oils. One highly preferredtriglyceride source which can be used herein is canola oil. Canola oilis a mixture of triglycerides having an appropriate chain lengthdistribution and degree of unsaturation of the respective acyl groups.Canola oil is a particularly desirable starting product in accordancewith the process of the present invention, for several reasons. Inparticular, its natural distribution of the chain lengths of therespective acyl groups has a notably high proportion of acyl groupscontaining 18 carbon atoms, thus avoiding the additional expenseincurred when using other commercial sources of C₁₈ fatty acids asstarting materials.

The triglyceride starting product can be hydrogenated, if desired, toconvert diunsaturated and triunsaturated acyl groups, particularly thosecontaining 18 carbon atoms, to their monounsaturated counterparts. It isnormally desirable that hydrogenation of mono-unsaturated acyl groups isminimized and even completely avoided. Saturated acyl groups can beobtained from normally saturated sources and mixed with unsaturated acylgroups. In some useful mixtures of acyl groups, no more than 10% ofunsaturated C₁₈ acyl groups are hydrogenated to their saturatedcounterparts. For some products, hydrogenation of diunsaturated andtriunsaturated C₁₈ acyl groups is preferably maximized, consistent withminimal formation of saturated C₁₈ groups. For instance, triunsaturatedacyl groups can be completely hydrogenated without achieving completehydrogenation of diunsaturated acyl groups.

Hydrogenation of the triglyceride starting product which maximizesmonounsaturated acyl groups can be readily achieved by maintaining anappropriate balance of the conditions of the hydrogenation reaction. Theprocess variables in the hydrogenation of triglycerides and the effectsof altering such variables, are generally quite familiar to those ofordinary skill in this art. In general, hydrogenation of thetriglyceride starting product can be carried out at a temperatureranging (broadly stated) between 170° C. and 205° C. and more preferablywithin a somewhat narrower range of from 185° C. to 195° C. The othersignificant process variable is the pressure of hydrogen within thehydrogenation reactor. In general, this pressure should be maintainedwithin a range (broadly stated) of from 2 psig to 20 psig, and morepreferably between from 5 psig and 15 psig.

Within these ranges of parameters, hydrogenation can be carried out witha particular view to the effects of these parameters. Lower hydrogenpressures in the reactor permit a greater degree of control of thereaction, particularly as to its selectivity. By “selectivity” is meantthe hydrogenation of diunsaturated and triunsaturated acyl groupswithout excessive hydrogenation of mono unsaturated acyl groups. On theother hand, higher hydrogen pressures afford less selectivity.Selectivity can be desirable in certain instances.

Higher hydrogenation temperatures are associated with faster rates ofhydrogenation and with greater selectivity of the hydrogenation.Conversely, lower hydrogenation temperatures are associated with lessselectivity (i.e. increased hydrogenation of the mono unsaturatedgroups), and particularly with slower hydrogenation rates in general.

These considerations are also balanced with considerations ofstereochemistry. More specifically, the presence of unsaturation in theacyl groups can lead to the formation of different stereoisomers in theacyl groups upon hydrogenation. The two possible stereoisomericconfigurations for unsaturated fatty acyl groups are known as the “cis”and the “trans” forms. The presence of the cis form is preferred, as itis associated with a lower melting point of the eventual product and,thus with greater fluidity, and better low temperature phase stabilityof clear compositions. Thus, another reason that canola oil is aparticularly preferred triglyceride starting product is that, as anaturally occurring material, the acyl groups present in thistriglyceride exhibit only the cis form. In the hydrogenation, higherhydrogen pressures are associated also with a decreased tendency of theacyl group to undergo configuration change from the cis form to thetrans form. Also, higher hydrogenation temperatures while favorable forsome reasons are also associated with higher conversion of cisunsaturation to the trans form. Products exhibiting satisfactoryproperties can be obtained by appropriate control of the hydrogenationconditions so as to afford both selectivity and control of thestereochemical configurations of the product.

The hydrogenation is carried out in the presence of a suitablehydrogenation catalyst. Such catalysts are well known and commerciallyavailable. They generally comprise nickel, palladium, ruthenium orplatinum, typically on a suitable catalyst support. A suitable catalystis a nickel based catalyst such as sold by Engelhard under the tradedesignation “N-545”®.

In one variation, the hydrogenation is carried out to an end point atwhich hydrogenation of the diunsaturation and triunsaturation in thetriglyceride product is maximized, while formation of saturated acylgroups is minimized. The progress of the hydrogenation reaction towardthe end point can readily be monitored by periodic measurement of theiodine value of the reaction mass. As the hydrogenation proceeds, theIodine Value decreases. For example, the hydrogenation reaction can bediscontinued when the Iodine Value reaches 95.

Other requirements for hydrogenation reactions are well known, such asthe types of reactor, cooling means to maintain the desired temperature,the provision of means for agitation effective to provide adequatecontact between the triglyceride and the hydrogen and catalyst, etc.

The triglyceride containing the desired acyl groups is reacted,typically by hydrolyzing or transesterification, to obtain the desiredfatty acyl groups as, e.g., the corresponding fatty acids and/or fattyacid esters. That is, the three ester bonds in the triglyceride arebroken so that the hydrogenated combination of acyl groups is convertedto a mixtures of fatty acids and/or esters having the same chain lengthdistribution as in the acyl groups, and having the distribution ofsaturation and unsaturation provided by the hydrogenation reaction.

Hydrolysis can be carried out under any of the suitable conditions knownin this art for hydrolysis of triglycerides into their fatty acidconstituents. In general, the triglyceride is reacted with hightemperature steam in a reactor, wherein the fatty acids are split offfrom glycerine, following which the steam is condensed to form anaqueous solution of glycerine and this solution is removed.Transesterification of the triglyceride can be carried out under any ofthe suitable conditions known in this art for transesterification oftriglycerides into their fatty acid ester constituents.

Once the fatty acid fraction is obtained, according to step a) of theinvention process, it is reacted (or also called esterified) withtriethanolamine for a period such that the condensation product obtainedcompound has an acid value (AV), measured by measured by titration ofthe condensation product with a standard KOH solution against aphenolphtaleine indicator according to ISO#53402, of less than 6.5.

For optimum softness benefit, it is preferred that the reactants arepresent in a molar ratio of fatty acid to triethanolamine of from 1:1 to2.5:1. More preferably, the reactants are present in a molar ratio offatty acid fraction to triethanolamine of from 1.4:1 to less than 1.8:1,preferably 1.5:1 when the aqueous medium in which they are to be usedcomprises a molar ratio of anionic surfactant to said softener compoundof the invention of at least 1:10.

On the other hand, when the aqueous medium in which they are to be usedcomprises a molar ratio of anionic surfactant to said softener compoundof the invention of less than 1:10, the reactants are preferably presentin a molar ratio of fatty acid fraction to triethanolamine of from 1.8:1to 2.2:1, preferably 2.0:1.

The esterification is carried out under conventional esterificationconditions, providing an acidic catalyst and providing for withdrawal ofbyproduct water of condensation. Preferably, a small amount generally upto 1.0 wt. % of the reactant (i.e. acids and amine), of hypo phosphorousacid (HPPA) is added to the esterification reaction mixture. The HPPA isbelieved to catalyze the reaction and as well to preserve or evenimprove the color of the product obtained in this reaction. Indeed,color control is critical to the appearance of clear softeningcompositions. Preferably, esterification is allowed to proceedcompletely such that all amine present is esterified with the fatty acidfraction. The Av is measured at different time interval on theesterified reaction product and the condensation reaction (also calledesterification reaction) is not stopped until the required AV isreached. This AV determination is made according to the ISO definedherein before.

After the required acid value for the condensation product has beenobtained, it is, according to step b) of the invention process, reactedwith an alkylating agent, in the presence or absence of a solvent.

The alkylation (also called quaternisation step) is carried out underconditions and with reactants generally familiar to those experienced inthis field. The quaternizing agent has the formula QA, wherein Q ispreferably methyl, benzyl, or ethyl, and A is an inert monovalent anion.

Preferably, the alkylating agent is selected from alkyl halides,sulphates, phosphates and carbonates, more preferably alkyl halides andsulphates. Suitable alkyl halide compounds for use as alkylating agentsin the present invention are selected from methyl chloride, benzylchloride.

Suitable alkyl sulphate compounds for use as alkylating agents in thepresent invention are the polyalkylsulphates selected fromdimethylsulphate and diethylsulphate. One of the more preferredalkylating agent is dimethylsulfate.

This alkylation step produces the quaternary ammonium ester of theinvention.

When the softener compound of the invention is formulated into clear ortranslucent compositions, it is most preferred to drive the quaternisingreaction as far to completion as possible, for the best clarity of thefinished composition. This is most particularly desirable when a highperfume level in the composition is present, e.g of more than 1.5% byweight of the composition of perfume and typically of 2.5% by weight.Such completion reaction can typically be done though longer reactiontimes, controlling temperatures and pressures, and using excessalkylating agent in the reaction. It is also most preferred to removeunreacted alkylating agent upon completion of the reaction to avoidmalodor and also potential safety issues (e.g. methyl chloride may beremoved by vacuum stripping).

C-Fabric Softening Composition

The compound of the invention is preferably incorporated in a fabricsoftening composition. Typical levels of incorporation are of from 1% to80% by weight, preferably from 5% to 75%, more preferably from 15% to70%, and even more preferably from 19% to 65%, by weight of thecomposition. Of course, mixtures of the above defined compound can beused herein. The softening composition according to the presentinvention can be in different form such as in liquid or solid form asdefined hereinafter.

When formulated as a liquid fabric softening composition, thecomposition may be in the form of a dispersion, e.g. aqueous dispersion,or also in the form of a clear composition. Accordingly, when in liquidform, the composition in addition to the softening compound of theinvention will also preferably comprises optional ingredients. When insuch liquid forms, it has been found most preferred, in order to improvethe stability of the softening composition according to the invention,that the softening compositions have a pH of from 3 to 4.

III. Optional Ingredients

(A)-Principal Solvent

A principal solvent is one of the preferred optional ingredient for usein the present composition invention. The compositions of the presentinvention may comprise a principal solvent system. This is particularlythe case when formulating liquid, clear fabric softening compositions.When employed, the principal solvent is typically used at a level ofless than 40% by weight, preferably from 6% to 35%, more preferably from8% to 25%, and even more preferably from 10% to 20%, by weight of thecomposition. The principal solvent is selected to minimize solvent odorimpact in the composition and to provide a low viscosity to the finalcomposition. For example, isopropyl alcohol is not very effective andhas a strong odor. n-Propyl alcohol is more effective, but also has adistinct odor. Several butyl alcohols also have odors but can be usedfor effective clarity/stability, especially when used as part of aprincipal solvent system to minimize their odor. The alcohols are alsoselected for optimum low temperature stability, that is they are able toform compositions that are liquid with acceptable low viscosities andtranslucent, preferably clear, down to about 40° F. (about 4.4° C.) andare able to recover after storage down to about 20° F. (about 6.7° C.).

The suitability of any principal solvent for the formulation of theliquid, concentrated, preferably clear, fabric softener compositionsherein with the requisite stability is surprisingly selective. Suitablesolvents can be selected based upon their octanol/water partitioncoefficient (P). Octanol/water partition coefficient of a principalsolvent is the ratio between its equilibrium concentration in octanoland in water. The partition coefficients of the principal solventingredients of this invention are conveniently given in the form oftheir logarithm to the base 10, logP.

The logP of many ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Information Systems,Inc. (Daylight CIS), Irvine, Calif., contains many, along with citationsto the original literature. However, the logP values are mostconveniently calculated by the “CLOGP” program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The “calculated logP” (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each ingredient, and takes into account thenumbers and types of atoms, the atom connectivity, and chemical bonding.These ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are preferably used insteadof the experimental logP values in the selection of the principalsolvent ingredients which are useful in the present invention. Othermethods that can be used to compute ClogP include, e.g., Crippen'sfragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21(1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf.Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J.Med. Chem.—Chim. Theor., 19, 71 (1984). The principal solvents hereinare selected from those having a ClogP of from about 0.15 to about 0.64,preferably from about 0.25 to about 0.62, and more preferably from about0.40 to about 0.60, said principal solvent preferably being at leastsomewhat asymmetric, and preferably having a melting, or solidification,point that allows it to be liquid at, or near room temperature. Solventsthat have a low molecular weight and are biodegradable are alsodesirable for some purposes. The more assymetric solvents appear to bevery desirable, whereas the highly symmetrical solvents such as1,7-heptanediol, or 1,4-bis(hydroxymethyl) cyclohexane, which have acenter of symmetry, appear to be unable to provide the essential clearcompositions when used alone, even though their ClogP values fall in thepreferred range.

The most preferred principal solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active.

Operable principal solvents are disclosed and listed below which haveClogP values which fall within the requisite range. These includemono-ols, C6 diols, C7 diols, octanediol isomers, butanediolderivatives, trimethylpentanediol isomers, ethylmethylpentanediolisomers, propyl pentanediol isomers, dimethylhexanediol isomers,ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers,nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, andaryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols andderivatives, C₃C₇ diol alkoxylated derivatives, aromatic diols, andunsaturated diols. These principal solvents are all disclosed in WO97/03169 having the title “CONCENTRATED, STABLE, PREFERABLY CLEAR,FABRIC SOFTENING COMPOSITION”.

Particularly preferred principal solvents include hexanediols such as1,2-hexanediol; and C8 diols such as 2-ethyl-1,3-hexanediol and2,2,4-trimethyl-1,3-pentanediol, ethoxylates of2,2,4-trimethyl-1,3-pentanediol and ethoxylates of2-ethyl-1,3-hexanediol; and 1,2 cyclohexanedimethanol.

Mixtures of principal solvent can also be used for the purpose of thepresent invention.

The principal solvents are desirably kept to the lowest levels that arefeasible in the present compositions for obtaining translucency orclarity. The presence of water exerts an important effect on the needfor the principal solvents to achieve clarity of these compositions. Thehigher the water content, the higher the principal solvent level(relative to the softener level) is needed to attain product clarity.Inversely, the less the water content, the less principal solvent(relative to the softener) is needed. Thus, at low water levels of from5% to 15%, the softener active-to-principal solvent weight ratio ispreferably from 55:45 to 85:15, more preferably from 60:40 to 80:20. Atwater levels of from 15% to 70%, the softener active-to-principalsolvent weight ratio is preferably from 45:55 to 70:30, more preferablyfrom 55:45 to 70:30. But at high water levels of from 70% to 80%, thesoftener active-to-principal solvent weight ratio is preferably from30:70 to 55:45, more preferably from 35:65 to 45:55. At even higherwater levels, the softener to principal solvent ratios should also beeven higher.

The compositions can also inherently provide improved perfume depositionof certain perfume components, especially for those that are poorlyfabric substantive as compared to conventional fabric softeningcompositions, especially when the perfume is added to the compositionsat, or near, room temperature.

More preferred for use herein is a combination of principal solvents.Most preferred combinations are 2,2,4-trimethyl-1,3-pentanediol (TMPD)in combination with 1,2 hexanediol. With the above preferredcombinations, lower total levels of solvents can be achieved therebyreducing the overall cost of the formulation. By the present principalsolvent combinations, it has been found that the resulting products havesurprising phase stability and fully recover from freezing down to 0° F.(−18° C.). The resulting products have also been surprisingly found tohave excellent water dispersibility. Furthermore, another advantage withthe use of such combination is their large availibility.

(B)

Low molecular weight water soluble solvents can also be used at levelsof from 0% to 12%, preferably from 1% to 10%, more preferably from 2% to8% by weight. The water soluble solvents cannot provide a clear productat the same low levels of the principal solvents described hereinbeforebut can provide clear product when the principal solvent is notsufficient to provide completely clear product. The presence of thesewater soluble solvents is therefore highly desirable. Such solventsinclude: ethanol; isopropanol; 1,2-propanediol; 1,3-propanediol;propylene carbonate; 1,4-cyclohexanedimethanol; etc. but do not includeany of the principal solvents (A). These water soluble solvents have agreater affinity for water in the presence of hydrophobic materials likethe softener compound than the principal solvents.

Among the above described co-solvent to be used in combination with theprincipal solvent, 1,4 cyclohexanedimethanol is a preferred co-solvent.

(C) Brighteners

The compositions herein can also optionally contain from 0.005% to 5% byweight of certain types of hydrophilic optical brighteners which alsoprovide a dye transfer inhibition action. If used, the compositionsherein will preferably comprise from 0.001% to 1% by weight of suchoptical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R¹ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the rinse added compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.

(D) Dispersibility Aids

Relatively concentrated compositions containing both saturated andunsaturated diester quaternary ammonium compounds can be prepared thatare stable without the addition of concentration aids. However, thecompositions of the present invention may require organic and/orinorganic concentration aids to go to even higher concentrations and/orto meet higher stability standards depending on the other ingredients.These concentration aids which typically can be viscosity modifiers maybe needed, or preferred, for ensuring stability under extreme conditionswhen particular softener active levels are used. The surfactantconcentration aids are typically selected from the group consisting of(1) single long chain alkyl cationic surfactants; (2) nonionicsurfactants; (3) amine oxides; (4) fatty acids; and (5) mixturesthereof. These aids are described in P&G Copending Application Ser. No.08/461,207, filed Jun. 5, 1995, Wahl et al., specifically on page 14,line 12 to page 20, line 12, which is herein incorporated by reference.When said dispersibility aids are present, the total level is from 2% to25%, preferably from 3% to 17%, more preferably from 4% to 15%, and evenmore preferably from 5% to 13% by weight of the composition. Thesematerials can either be added as part of the active softener rawmaterial, (I), e.g., the mono-long chain alkyl cationic surfactantand/or the fatty acid which are reactants used to form the biodegradablefabric softener active as discussed hereinbefore, or added as a separatecomponent. The total level of dispersibility aid includes any amountthat may be present as part of component (I).

(1) Mono-Alkyl Cationic Quaternary Ammonium Compound

When the mono-alkyl cationic quaternary ammonium compound is present, itis typically present at a level of from 2% to 25%, preferably from 3% to17%, more preferably from 4% to 15%, and even more preferably from 5% to13% by weight of the composition, the total mono-alkyl cationicquaternary ammonium compound being at least at an effective level.

Such mono-alkyl cationic quaternary ammonium compounds useful in thepresent invention are, preferably, quaternary ammonium salts of thegeneral formula:

[R⁴N+(R⁵)₃]X⁻

wherein

R⁴ is C₈-C₂₂ alkyl or alkenyl group, preferably C₁₀-C₁₈ alkyl or alkenylgroup; more preferably C₁₀-C₁₄ or C₁₆-C₁₈ alkyl or alkenyl group;

each R⁵ is a C₁-C₆ alkyl or substituted alkyl group (e.g., hydroxyalkyl), preferably C₁-C₃ alkyl group, e.g., methyl (most preferred),ethyl, propyl, and the like, a benzyl group, hydrogen, a polyethoxylatedchain with from 2 to 20 oxyethylene units, preferably from 2.5 to 13oxyethylene units, more preferably from 3 to 10 oxyethylene units, andmixtures thereof; and

X⁻ is as defined hereinbefore for (Formula (I)).

Especially preferred dispersibility aids are monolauryl trimethylammonium chloride and monotallow trimethyl ammonium chloride availablefrom Witco under the trade names Adogen® 412 and Adogen® 471, monooleylor monocanola trimethyl ammonium chloride available from Witco under thetradename Adogen® 417, monococonut trimethyl ammonium chloride availablefrom Witco under the trade name Adogen® 461, and monosoya trimethylammonium chloride available from Witco under the trade name Adogen® 415.

The R⁴ group can also be attached to the cationic nitrogen atom througha group containing one, or more, ester, amide, ether, amine, etc.,linking groups which can be desirable for increased concentratability ofcomponent (I), etc. Such linking groups are preferably within from oneto three carbon atoms of the nitrogen atom.

Mono-alkyl cationic quaternary ammonium compounds also include C₈-C₂₂alkyl choline esters. The preferred dispersibility aids of this typehave the formula:

R¹C(O)—O—CH₂CH₂N⁺(R)₃X⁻

wherein R¹, R and X⁻ are as defined previously.

Highly preferred dispersibility aids include C₁₂-C₁₄ coco choline esterand C₁₆-C₁₈ tallow choline ester.

Suitable biodegradable single-long-chain alkyl dispersibility aidscontaining an ester linkage in the long chains are described in U.S.Pat. No. 4,840,738, Hardy and Walley, issued Jun. 20, 1989, said patentbeing incorporated herein by reference.

When the dispersibility aid comprises alkyl choline esters, preferablythe compositions also contain a small amount, preferably from 2% to 5%by weight of the composition, of organic acid. Organic acids aredescribed in European Patent Application No. 404,471, Machin et al.,published on Dec. 27, 1990, supra, which is herein incorporated byreference. Preferably the organic acid is selected from the groupconsisting of glycolic acid, acetic acid, citric acid, and mixturesthereof.

Ethoxylated quaternary ammonium compounds which can serve as thedispersibility aid include ethylbis(polyethoxy ethanol)alkylammoniumethyl-sulfate with 17 moles of ethylene oxide, available under the tradename Variquat® 66 from Witco Corporation; polyethylene glycol (15)oleammonium chloride, available under the trade name Ethoquad® 0/25 fromAkzo; and polyethylene glycol (15) cocomonium chloride, available underthe trade name Ethoquad® C/25 from Akzo.

Quaternary compounds having only a single long alkyl chain, can protectthe cationic softener from interacting with anionic surfactants and/ordetergent builders that are carried over into the rinse from the washsolution.

(2) Nonionic Surfactant (Alkoxylated Materials)

Suitable nonionic surfactants to serve as the viscosity/dispersibilitymodifier include addition products of ethylene oxide and, optionally,propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc.They are referred to herein as ethoxylated fatty alcohols, ethoxylatedfatty acids, and ethoxylated fatty amines.

Any of the alkoxylated materials of the particular type describedhereinafter can be used as the nonionic surfactant. In general terms,the nonionics herein, when used alone, in liquid compositions are at alevel of from 0% to 5%, preferably from 0.1% to 5%, more preferably from0.2% to 3%. Suitable compounds are substantially water-solublesurfactants of the general formula:

R²—Y—(C₂H₄O)_(Z)—C₂H₄OH

wherein R² for both solid and liquid compositions is selected from thegroup consisting of primary, secondary and branched chain alkyl and/oracyl hydrocarbyl groups; primary, secondary and branched chain alkenylhydrocarbyl groups; and primary, secondary and branched chain alkyl- andalkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groupshaving a hydrocarbyl chain length of from 8 to 20, preferably from 10 to18 carbon atoms. More preferably the hydrocarbyl chain length for liquidcompositions is from 16 to 18 carbon atoms and for solid compositionsfrom 10 to 14 carbon atoms. In the general formula for the ethoxylatednonionic surfactants herein, Y is typically —O—, —C(O)O—, —C(O)N(R)—, or—C(O)N(R)R—, preferably —O—, and in which R², and R, when present, havethe meanings given hereinbefore, and/or R can be hydrogen, and z is atleast 8, preferably at least 10-11. Performance and, usually, stabilityof the softener composition decrease when fewer ethoxylate groups arepresent.

The nonionic surfactants herein are characterized by an HLB(hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to15. Of course, by defining R² and the number of ethoxylate groups, theHLB of the surfactant is, in general, determined. However, it is to benoted that the nonionic ethoxylated surfactants useful herein, forconcentrated liquid compositions, contain relatively long chain R²groups and are relatively highly ethoxylated. While shorter alkyl chainsurfactants having short ethoxylated groups can possess the requisiteHLB, they are not as effective herein.

Nonionic surfactants as the viscosity/dispersibility modifiers arepreferred over the other modifiers disclosed herein for compositionswith higher levels of perfume.

Examples of nonionic surfactants follow. The nonionic surfactants ofthis invention are not limited to these examples. In the examples, theinteger defines the number of ethoxy (EO) groups in the molecule.

(3) Amine Oxides

Suitable amine oxides include those with one alkyl or hydroxyalkylmoiety of 8 to 22 carbon atoms, preferably from 10 to 18 carbon atoms,more preferably from 8 to 14 carbon atoms, and two alkyl moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups with 1 to 3 carbon atoms.

Examples include dimethyloctylamine oxide, diethyldecylamine oxide,bis-2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide,dipropyl-tetradecylamine oxide, methylethylhexadecylamine oxide,dimethyl-2-HYDROXYOCTADECYLAMINE oxide, and coconut fatty alkyldimethylamine oxide.

(E) Stabilizers

Stabilizers can be present in the compositions of the present invention.The term “stabilizer,” as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% to 2%,preferably from 0.01% to 0.2%, more preferably from 0.035% to 0.1% forantioxidants, and more preferably from 0.01% to 0.2% for reductiveagents. These assure good odor stability under long term storageconditions. Antioxidants and reductive agent stabilizers are especiallycritical for unscented or low scent products (no or low perfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox® S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox®-6; butylated hydroxytoluene, available from UOPProcess Division under the trade name Sustane® BHT; tertiarybutylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ;natural tocopherols, Eastman Chemical Products, Inc., as Tenox®GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,Inc., as BHA; long chain esters (C₈-C₂₂) of gallic acid, e.g., dodecylgallate; Irganox® 1010; Irganox® 1035; Irganox® B 1171; Irganox® 1425;Irganox® 3114; Irganox® 3125; and mixtures thereof; preferablyIrganox®3125, Irganox® 1425, Irganox® 3114, and mixtures thereof; morepreferably Irganox® 3125 alone or mixed with citric acid and/or otherchelators such as isopropyl citrate, Dequest® 2010, available fromMonsanto with a chemical name of 1-hydroxyethylidene-1, 1-diphosphonicacid (etidronic acid), and Tiron®, available from Kodak with a chemicalname of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®,available from Aldrich with a chemical name ofdiethylenetriaminepentaacetic acid.

(F) Soil Release Agent

In the present invention, an optional soil release agent can be added.The addition of the soil release agent can occur in combination with thepremix, in combination with the acid/water seat, before or afterelectrolyte addition, or after the final composition is made. Thesoftening composition prepared by the process of the present inventionherein can contain from 0% to 10%, preferably from 0.2% to 5%, of a soilrelease agent. Preferably, such a soil release agent is a polymer.Polymeric soil release agents useful in the present invention includecopolymeric blocks of terephthalate and polyethylene oxide orpolypropylene oxide, and the like.

A preferred soil release agent is a copolymer having blocks ofterephthalate and polyethylene oxide. More specifically, these polymersare comprised of repeating units of ethylene terephthalate andpolyethylene oxide terephthalate at a molar ratio of ethyleneterephthalate units to polyethylene oxide terephthalate units of from25:75 to 35:65, said polyethylene oxide terephthalate containingpolyethylene oxide blocks having molecular weights of from 300 to 2000.The molecular weight of this polymeric soil release agent is in therange of from 5,000 to 55,000.

Another preferred polymeric soil release agent is a crystallizablepolyester with repeat units of ethylene terephthalate units containingfrom 10% to 15% by weight of ethylene terephthalate units together withfrom 10% to 50% by weight of polyoxyethylene terephthalate units,derived from a polyoxyethylene glycol of average molecular weight offrom 300 to 6,000, and the molar ratio of ethylene terephthalate unitsto polyoxyethylene terephthalate units in the crystallizable polymericcompound is between 2:1 and 6:1. Examples of this polymer include thecommercially available materials Zelcon 4780® (from Dupont) and MileaseT® (from ICI).

Highly preferred soil release agents are polymers of the genericformula:

in which each X can be a suitable capping group, with each X typicallybeing selected from the group consisting of H, and alkyl or acyl groupscontaining from 1 to 4 carbon atoms. p is selected for water solubilityand generally is from 6 to 113, preferably from 20 to 50. u is criticalto formulation in a liquid composition having a relatively high ionicstrength. There should be very little material in which u is greaterthan 10. Furthermore, there should be at least 20%, preferably at least40%, of material in which u ranges from 3 to 5.

The R¹⁴ moieties are essentially 1,4-phenylene moieties. As used herein,the term “the R¹⁴ moieties are essentially 1,4-phenylene moieties”refers to compounds where the R¹⁴ moieties consist entirely of1,4-phenylene moieties, or are partially substituted with other aryleneor alkarylene moieties, alkylene moieties, alkenylene moieties, ormixtures thereof. Arylene and alkarylene moieties which can be partiallysubstituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene,1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, andmixtures thereof. Alkylene and alkenylene moieties which can bepartially substituted include 1,2-propylene, 1,4-butylene,1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene,1,4-cyclohexylene, and mixtures thereof.

For the R¹⁴ moieties, the degree of partial substitution with moietiesother than 1,4-phenylene should be such that the soil release propertiesof the compound are not adversely affected to any great extent.Generally the degree of partial substitution which can be tolerated willdepend upon the backbone length of the compound, i.e., longer backbonescan have greater partial substitution for 1,4-phenylene moieties.Usually, compounds where the R¹⁴ comprise from 50% to 100% 1,4-phenylenemoieties (from 0% to 50% moieties other than 1,4-phenylene) haveadequate soil release activity. For example, polyesters made accordingto the present invention with a 40:60 mole ratio of isophthalic(1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soilrelease activity. However, because most polyesters used in fiber makingcomprise ethylene terephthalate units, it is usually desirable tominimize the degree of partial substitution with moieties other than1,4-phenylene for best soil release activity. Preferably, the R¹⁴moieties consist entirely of (i.e., comprise 100%) 1,4-phenylenemoieties, i.e., each R¹⁴ moiety is 1,4-phenylene.

For the R¹⁵ moieties, suitable ethylene or substituted ethylene moietiesinclude ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene,3-methoxy-1,2-propylene, and mixtures thereof. Preferably, the R¹⁵moieties are essentially ethylene moieties, 1,2-propylene moieties, ormixtures thereof. Inclusion of a greater percentage of ethylene moietiestends to improve the soil release activity of compounds. Surprisingly,inclusion of a greater percentage of 1,2-propylene moieties tends toimprove the water solubility of compounds.

Therefore, the use of 1,2-propylene moieties or a similar branchedequivalent is desirable for incorporation of any substantial part of thesoil release component in the liquid fabric softener compositions.Preferably, from 75% to 100%, are 1,2-propylene moieties.

The value for each p is at least 6, and preferably is at least 10. Thevalue for each n usually ranges from 12 to 113. Typically the value foreach p is in the range of from 12 to 43.

A more complete disclosure of soil release agents is contained in U.S.Pat. Nos.: 4,661,267; 4,711,730; 4,749,596; 4,818,569; 4,877,896;4,956,447; and 4,976,879, all of said patents being incorporated hereinby reference.

These soil release agents can also act as scum dispersants.

(G) Scum Dispersant

In the present invention, the premix can be combined with an optionalscum dispersant, other than the soil release agent, and heated to atemperature at or above the melting point(s) of the components.

The preferred scum dispersants herein are formed by highly ethoxylatinghydrophobic materials. The hydrophobic material can be a fatty alcohol,fatty acid, fatty amine, fatty acid amide, amine oxide, quaternaryammonium compound, or the hydrophobic moieties used to form soil releasepolymers. The preferred scum dispersants are highly ethoxylated, e.g.,more than 17, preferably more than 25, more preferably more than 40,moles of ethylene oxide per molecule on the average, with thepolyethylene oxide portion being from 76% to 97%, preferably from 81% to94%, of the total molecular weight.

The level of scum dispersant is sufficient to keep the scum at anacceptable, preferably unnoticeable to the consumer, level under theconditions of use, but not enough to adversely affect softening. Forsome purposes it is desirable that the scum is nonexistent. Depending onthe amount of anionic or nonionic detergent, etc., used in the washcycle of a typical laundering process, the efficiency of the rinsingsteps prior to the introduction of the compositions herein, and thewater hardness, the amount of anionic or nonionic detergent surfactantand detergency builder (especially phosphates and zeolites) entrapped inthe fabric (laundry) will vary. Normally, the minimum amount of scumdispersant should be used to avoid adversely affecting softeningproperties. Typically scum dispersion requires at least 2%, preferablyat least 4% (at least 6% and preferably at least 10% for maximum scumavoidance) based upon the level of softener active. However, at levelsof 10% (relative to the softener material) or more, one risks loss ofsoftening efficacy of the product especially when the fabrics containhigh proportions of nonionic surfactant which has been absorbed duringthe washing operation.

Preferred scum dispersants are: Brij 700®; Varonic U-250®; GenapolT-500®) Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.

(H) Bactericides

Examples of bactericides used in the compositions of this inventioninclude glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diolsold by Inolex Chemicals, located in Philadelphia, Pa., under the tradename Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-oneand 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company underthe trade name Kathon 1 to 1,000 ppm by weight of the agent.

(I) Perfume

The present invention can contain any softener compatible perfume.Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138, said patentbeing incorporated herein by reference.

As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds.

Examples of perfume ingredients useful in the perfumes of the presentinvention compositions include, but are not limited to, hexyl cinnamicaldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate;terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol;2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol;3,7-dimethyl-trans-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol;3,7-dimethyl-1-octanol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

Additional examples of fragrance materials include, but are not limitedto, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil;dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate;beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;Schiff's base of4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methylanthranilate; cyclic ethyleneglycol diester of tridecandioic acid;3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;ionone beta; petitgrain; methyl cedrylone;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;16-HYDROXY-9-hexadecenoic acid lactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol;5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexylacetate; patchouli; olibanum resinoid; labdanum; vetivert; copaibabalsam; fir balsam; and condensation products of: hydroxycitronellal andmethyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehydeand indol; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehydeand methyl anthranilate.

More examples of perfume components are geraniol; geranyl acetate;linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellylacetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol;terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethylacetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzylbenzoate; styrallyl acetate; dimethylbenzylcarbinol;trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononylacetate; vetiveryl acetate; vetiverol;2-methyl-3-(p-tert-butylphenyl)-propanal;2-methyl-3-(p-isopropylphenyl)-propanal;3-(p-tert-butylphenyl)-propanal;4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal;n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehydedimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedrylmethylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methylionones; isomethyl ionomes; irones; cis-3-hexenol and esters thereof;indane musk fragrances; tetralin musk fragrances; isochroman muskfragrances; macrocyclic ketones; macrolactone musk fragrances; ethylenebrassylate.

The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

Perfume can be present at a level of from 0% to 10%, preferably from0.1% to 5%, and more preferably from 0.2% to 3%, by weight of thefinished composition. Fabric softener compositions of the presentinvention provide improved fabric perfume deposition.

(J) Chelating Agents

The compositions and processes herein can optionally employ one or morecopper and/or nickel chelating agents (“chelators”). Such water-solublechelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures thereof, all as hereinafter defined. Thewhiteness and/or brightness of fabrics are substantially improved orrestored by such chelating agents and the stability of the materials inthe compositions are improved.

Amino carboxylates useful as chelating agents herein includeethylenediaminetetraacetates (EDTA),N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA),ethylenediamine tetraproprionates, ethylenediamine-N,N′-diglutamates,2-hyroxypropylenediamine-N,N′-disuccinates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates(DETPA), and ethanoldiglycines, including their water-soluble salts suchas the alkali metal, ammonium, and substituted ammonium salts thereofand mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates),diethylenetriamine-N,N,N′,N″,N″-pentakis(methane phosphonate) (DETMP)and 1-hydroxyethane-1,1-diphosphonate (HEDP). Preferably, these aminophosphonates to not contain alkyl or alkenyl groups with more than 6carbon atoms.

The chelating agents are typically used in the present rinse process atlevels from 2 ppm to 25 ppm, for periods from 1 minute up to severalhours' soaking.

The preferred EDDS chelator used herein (also known asethylenediamine-N,N′-disuccinate) is the material described in U.S. Pat.No. 4,704,233, cited hereinabove, and has the formula (shown in freeacid form):

As disclosed in the patent, EDDS can be prepared using maleic anhydrideand ethylenediamine. The preferred biodegradable [S,S] isomer of EDDScan be prepared by reacting L-aspartic acid with 1,2-dibromoethane. TheEDDS has advantages over other chelators in that it is effective forchelating both copper and nickel cations, is available in abiodegradable form, and does not contain phosphorus. The EDDS employedherein as a chelator is typically in its salt form, i.e., wherein one ormore of the four acidic hydrogens are replaced by a water-soluble cationM, such as sodium, potassium, ammonium, triethanolammonium, and thelike. As noted before, the EDDS chelator is also typically used in thepresent rinse process at levels from 2 ppm to 25 ppm for periods from 1minute up to several hours' soaking. At certain pH's the EDDS ispreferably used in combination with zinc cations.

As can be seen from the foregoing, a wide variety of chelators can beused herein. Indeed, simple polycarboxylates such as citrate,oxydisuccinate, and the like, can also be used, although such chelatorsare not as effective as the amino carboxylates and phosphonates, on aweight basis. Accordingly, usage levels may be adjusted to take intoaccount differing degrees of chelating effectiveness. The chelatorsherein will preferably have a stability constant (of the fully ionizedchelator) for copper ions of at least 5, preferably at least 7.Typically, the chelators will comprise from 0.5% to 10%, more preferablyfrom 0.75% to 5%, by weight of the compositions herein. Preferredchelators include DETMP, DETPA, NTA, EDDS and mixtures thereof.

(K)-Enzyme

The compositions and processes herein can optionally employ one or moreenzymes such as lipases, proteases, cellulase, amylases and peroxidases.A preferred enzyme for use herein is a cellulase enzyme. Indeed, thistype of enzyme will further provide a color care benefit to the treatedfabric. Cellulases usable herein include both bacterial and fungaltypes, preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212—producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitablecellulases are also disclosed in WO 91/17243 to Novo, WO 96/34092, WO96/34945 and EP-A-0,739,982. In practical terms for current commercialpreparations, typical amounts are up to 5 mg by weight, more typically0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.Stated otherwise, the compositions herein will typically comprise from0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzymepreparation. In the particular cases where activity of the enzymepreparation can be defined otherwise such as with cellulases,corresponding activity units are preferred (e.g. CEVU or cellulaseEquivalent Viscosity Units). For instance, the compositions of thepresent invention can contain cellulase enzymes at a level equivalent toan activity from about 0.5 to 1000 CEVU/gram of composition. Cellulaseenzyme preparations used for the purpose of formulating the compositionsof this invention typically have an activity comprised between 1,000 and10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.

(L) Other Optional Ingredients

The present invention can include optional components conventionallyused in textile treatment compositions, for example: colorants;preservatives; surfactants; anti-shrinkage agents; fabric crispingagents; spotting agents; germicides; fungicides; anti-oxidants such asbutylated hydroxy toluene, anti-corrosion agents, and the like.

The present invention can also include other compatible ingredients,including those as disclosed in copending applications Ser. No.08/372,068, filed Jan. 12, 1995, Rusche, et al.; Ser. No. 08/372,490,filed Jan. 12, 1995, Shaw, et al.; and Ser. No. 08/277,558, filed Jul.19, 1994, Hartman, et al., incorporated herein by reference.

Fabric Softener Processing

Also within the scope of the present invention, is a process forpreparing a premix composition and a fabric softener composition fromthe premix. According to another aspect of the invention, the premixcomposition comprises a fabric softener compound of the invention and aneffective amount of a component selected from the group consisting ofprincipal solvents, low molecular weight water soluble solvents, watersoluble calcium salt, water soluble magnesium salt, perfume, andmixtures thereof.

The use of a principal solvent allows the preparation of premixescomprising the softener active (from 55% to 85%, preferably from 60% to80%, more preferably from 65% to 75%, by weight of the premix); theprincipal solvent (from 10% to 30%, preferably from 13% to 25%, morepreferably from 15% to 20%, by weight of the premix); and optionally,the water soluble solvent (from 5% to 20%, preferably from 5% to 17%,more preferably from 5% to 15%, by weight of the premix). These premixescontain the desired amount of fabric softening active and sufficientprincipal solvent and, optionally, solvent to give the premix thedesired viscosity for the desired temperature range. Typical viscositiessuitable for processing are less than 1000 cps, preferably less than 500cps, more preferably less than 300 cps. Use of low temperatures improvessafety, by minimizing solvent vaporization, minimizes the degradationand/or loss of materials such as the biodegradable fabric softeneractive, perfumes, etc., and reduces the need for heating, thus saving onthe expenses for processing. The result is improved environmental impactand safety from the manufacturing operation.

Examples of premixes and processes using them include premixes whichtypically contain from 55% to 85%, preferably from 60% to 80%, morepreferably from 65% to 75%, of fabric softener active as exemplified inthe Examples, mixed with from 10% to 30%, preferably from 13% to 25%,more preferably from 15% to 20%, of principal solvent such as1,2-hexanediol, and from 5% to 20%, preferably from 5% to 15%, of watersoluble solvent like ethanol and/or isopropanol and/or hexylene glycol.

These premixes can be used to formulate fabric softening compositions inprocesses comprising the steps of:

1. Make premix of fabric softening active, 11% ethanol, and 17%principal solvent, let cool to ambient temperature.

2. Mix perfume in the premix.

3. Make up water seat of water and HCl at ambient temperature.Optionally add chelant and/or antioxidant.

4. Add premix to water under good agitation.

5. Trim with CaCl₂ solution to desired viscosity.

6. Add dye solution to get desired color.

Typically, the pH of the premix in water is adjusted to from 1.5 to 5.The diester quaternary fabric softening actives (DEQAs); the principalsolvents and, optionally, the water soluble solvents, can be formulatedas premixes which can be used to prepare fabric softening compositions.

Solid Compositions

1. Solid particulate compositions

As discussed hereinbefore, the invention also comprises solidparticulate composition comprising:

(A) from 50% to 95%, preferably from 60% to 90%, of said biodegradablefabric softening active;

(B) optionally, from 0% to 30%, preferably from 3% to 15%, ofdispersibility modifier; and

(D) from 0% to 10% of a pH modifier.

Optional pH Modifier

Since the biodegradable ester fabric softener actives are somewhatlabile to hydrolysis, it is preferable to include optional pH modifiersin the solid particulate composition to which water is to be added, toform stable dilute or concentrated liquid softener compositions. Saidstable liquid compositions should have a pH (neat) of from 2 to 5,preferably from 2 to 4.5, more preferably from 2 to 4, and mostpreferably from 3 to 4.

The pH can be adjusted by incorporating a solid, water soluble Bronstedacid. Examples of suitable Bronsted acids include inorganic mineralacids, such as boric acid, sodium bisulfate, potassium bisulfate, sodiumphosphate monobasic, potassium phosphate monobasic, and mixturesthereof; organic acids, such as citric acid, fumaric acid, maleic acid,malic acid, tannic acid, gluconic acid, glutamic acid, tartaric acid,glycolic acid, chloroacetic acid, phenoxyacetic acid, 1,2,3,4-butanetetracarboxylic acid, benzene sulfonic acid, benzene phosphonic acid,ortho-toluene sulfonic acid, para-toluene sulfonic acid, phenol sulfonicacid, naphthalene sulfonic acid, oxalic acid, 1,2,4,5-pyromellitic acid,1,2,4-trimellitic acid, adipic acid, benzoic acid, phenylacetic acid,salicylic acid, succinic acid, and mixtures thereof; and mixtures ofmineral inorganic acids and organic acids. Preferred pH modifiers arecitric acid, gluconic acid, tartaric acid, 1,2,3,4-butanetetracarboxylic acid, malic acid, and mixtures thereof.

Optionally, materials that can form solid clathrates such ascyclodextrins and/or zeolites, etc., can be used as adjuvants in thesolid particulate composition as host carriers of concentrated liquidacids and/or anhydrides, such as acetic acid, HCl, sulfuric acid,phosphoric acid, nitric acid, carbonic acid, etc. An example of suchsolid clatherates is carbon dioxide adsorbed in zeolite A, as disclosedin U.S. Pat. No. 3,888,998 and U.S. Pat. No. 4,007,134 both of saidpatents being incorporated herein by reference. Examples of inclusioncomplexes of phosphoric acid, sulfuric acid, and nitric acid, andprocess for their preparation are disclosed in U.S. Pat. No. 4,365,061said patent being incorporated herein by reference.

When used, the pH modifier is typically used at a level of from 0.01% to10%, preferably from 0.1% to 5%, by weight of the composition.

Preparation of Solid Particulate Granular Fabric Softener

The granules can be formed by preparing a melt, solidifying it bycooling, and then grinding and sieving to the desired size. In athree-component mixture, e.g., nonionic surfactant, single-long-chaincationic, and DEQA, it is more preferred, when forming the granules, topre-mix the nonionic surfactant and the more soluble single-long-chainalkyl cationic compound before mixing in a melt of the diesterquaternary ammonium cationic compound.

It is highly preferred that the primary particles of the granules have adiameter of from 50 to 1,000, preferably from 50 to 400, more preferablyfrom 50 to 200, microns. The granules can comprise smaller and largerparticles, but preferably from 85% to 95%, more preferably from 95% to100%, are within the indicated ranges. Smaller and larger particles donot provide optimum emulsions/dispersions when added to water. Othermethods of preparing the primary particles can be used including spraycooling of the melt. The primary particles can be agglomerated to form adust-free, non-tacky, free-flowing powder. The agglomeration can takeplace in a conventional agglomeration unit (i.e., Zig-Zag Blender,Lodige) by means of a water-soluble binder. Examples of water-solublebinders useful in the above agglomeration process include glycerol,polyethylene glycols, polymers such as PVA, polyacrylates, and naturalpolymers such as sugars.

The flowability of the granules can be improved by treating the surfaceof the granules with flow improvers such as clay, silica or zeoliteparticles, water-soluble inorganic salts, starch, etc.

Method of Use

Water can be added to the particulate, solid, granular compositions toform dilute or concentrated liquid softener compositions for lateraddition to the rinse cycle of the laundry process with a concentrationof said biodegradable cationic softening compound of from 0.5% to 50%,preferably from 1% to 35%, more preferably from 4% to 32% by weight. Theparticulate, rinse-added solid composition (1) can also be used directlyin the rinse bath to provide adequate usage concentration (e.g., from 10to 1,000 ppm, preferably from 50 to 500 ppm, of total softener activeingredient). The liquid compositions can be added to the rinse toprovide the same usage concentrations.

The water temperature for preparation should be from 20° C. to 90° C.,preferably from 25° C. to 80° C. Single-long-chain alkyl cationicsurfactants as the viscosity/dispersibility modifier at a level of from0% to 15%, preferably from 3% to 15%, more preferably from 5% to 15%, byweight of the composition, are preferred for the solid composition.Nonionic surfactants at a level of from 5% to 20%, preferably from 8% to15%, as well as mixtures of these agents can also serve effectively asthe viscosity/dispersibility modifier.

The emulsified/dispersed particles, formed when the said granules areadded to water to form aqueous concentrates, typically have an averageparticle size of less than 10 microns, preferably less than 2 microns,and more preferably from 0.2 to 2 microns, in order that effectivedeposition onto fabrics is achieved. The term “average particle size,”in the context of this specification, means a number average particlesize, i.e., more than 50% of the particles have a diameter less than thespecified size.

Particle size for the emulsified/dispersed particles is determinedusing, e.g., a Malvern particle size analyzer.

Depending upon the particular selection of nonionic and cationicsurfactant, it may be desirable in certain cases, when using the solidsto prepare the liquid, to employ an efficient means for dispersing andemulsifying the particles (e.g., blender).

Solid particulate compositions used to make liquid compositions can,optionally, contain electrolytes, perfume, antifoam agents, flow aids(e.g., silica), dye, preservatives, and/or other optional ingredientsdescribed hereinbefore.

The benefits of adding water to the particulate solid composition toform aqueous compositions to be added later to the rinse bath includethe ability to transport less weight thereby making shipping moreeconomical, and the ability to form liquid compositions similar to thosethat are normally sold to consumers, e.g., those that are describedherein, with lower energy input (i.e., less shear and/or lowertemperature). Furthermore, the particulate granular solid fabricsoftener compositions, when sold directly to the consumers, have lesspackaging requirements and smaller, more disposable containers. Theconsumers will then add the compositions to available, more permanent,containers, and add water to pre-dilute the compositions, which are thenready for use in the rinse bath, just like the liquid compositionsherein. The liquid form is easier to handle, since it simplifiesmeasuring and dispensing.

2. Dryer Activated Compositions

The present invention also relates to improved solid dryer-activatedfabric softener compositions which are either (A) incorporated intoarticles of manufacture, e.g., on a substrate, or, are (B) in the formof particles similar to those disclosed above. (including, whereappropriate, agglomerates, pellets, and tablets of said particles). Suchcompositions typically contain from 10% to 95% of fabric softeningagent.

A. Substrate Articles

In preferred embodiments, the present invention encompasses articles ofmanufacture. Representative articles are those that are adapted for useto provide unique perfume benefits and to soften fabrics in an automaticlaundry dryer, of the types disclosed in U.S. Pat. Nos.: 3,989,631;4,055,248; 4,073,996; 4,022,938; 4,764,289; 4,808,086; 4,103,047;3,736,668; 3,701,202; 3,634,947; 3,633,538; and 3,435,537; and4,000,340,, all of said patents being incorporated herein by reference.

Typical articles of manufacture of this type include articlescomprising:

I. a fabric conditioning composition comprising from 30% to 95% ofnormally solid, dryer softenable fabric softening agent comprising saidbiodegradable fabric softening active; and

II. a dispensing means which provides for release of an effective amountof said composition including an effective amount of ii, sufficient toprovide odor control, to fabrics in an automatic laundry dryer atautomatic laundry dryer operating temperatures, e.g., from 35° C. to115° C.

When the dispensing means is a flexible substrate, e.g., in sheetconfiguration, the fabric conditioning composition is releasably affixedon the substrate to provide a weight ratio of conditioning compositionto dry substrate ranging from 10:1 to 0.5:1, preferably from 5:1 to 1:1.

The solid fabric softener compositions herein can include cationic andnonionic fabric softener actives used in combination with each other.

D-EXAMPLES

The synthesis of the fabric softening compound of the present inventionis further illustrated in the following Synthesis Examples. TheseSynthesis Examples are provided for purposes of illustration only.

Fatty Acid Compound Synthesis Example A

1,300 grams of food grade (refined, bleached, degummed) canola oil andapproximately 6.5 grams of a commercial nickel hydrogenation catalyst(Engelhard, “N-545”®) corresponding to approximately 0.13 wt. % Ni, areplaced in a hydrogenation reactor which is equipped with stirrer. Thereactor is sealed and evacuated. The contents are heated to 170° C. andhydrogen is fed into the reactor. Stirring at 450 rpm is maintainedthroughout the reaction. After 10 minutes the temperature in the reactoris 191° C. and the hydrogen pressure is 11 psig. The temperature is heldat 190° C. After 127 minutes from when the hydrogen feed began, thehydrogen pressure is 10 psig. A sample of the reaction mass is drawn andfound to have an Iodine Value of 78.0 and a cis:trans ratio of 1.098.After another 20 minutes at 190° C., the hydrogen pressure is 9.8 psig.The hydrogen feed is discontinued and the reactor contents cooled withstirring. The final reaction product has an Iodine Value of 74.5 and acis:trans ratio of 1.35.

The product that forms in the reactor is removed and filtered. It has acloud point of 22.2° C. The chain length distributions of the acylsubstituents on the sample taken at 127 minutes, and of the finalproduct, are determined to be as shown in Table 1 in which “sat.” meanssaturated, and “mono” and “di” means monounsaturated and diunsaturated,respectively.

TABLE 1 Approximate Percent (mol.) Chain length Sample @ 127 min.Product C14-sat. 0.1 0.1 C16-sat. 4.7 4.6 C16-mono. 0.4 0.4 C18-sat. 8.913.25 C18-mono. 77.0  73.8  C18-di. 4.5 3.1 C20-sat. 0.7 0.75 C-20-mono.2.1 2.0 Other 1.6 2.0

Fatty Acid Compound Synthesis Example B

1,300 grams of food grade canola oil and 5.2 grams of Engelhard “N-545”® nickel hydrogenation catalyst are placed in a hydrogenation reactorwhich is equipped with a stirrer. The reactor is sealed and evacuated.The contents are heated to 175° C. and hydrogen is fed into the reactor.Stirring is maintained at 450 rpm throughout the course of reaction.After 5 minutes the temperature in the reactor is 190° C. and thehydrogen pressure is 7 psig.

The temperature is held at 190° C. After 125 minutes from the start ofthe hydrogen feed, the hydrogen pressure is 7 psig. A sample of thereaction mass is drawn and found to have an Iodine Value of 85.4. Afteranother 20 minutes at 190° C., the hydrogen pressure is 6 psig. Thehydrogen feed is discontinued and the reactor contents cooled withstirring. The final reaction product has an Iodine Value of 80.0. Theproduct that forms in the reactor is removed and filtered. It has acloud point of 18.6° C.

Fatty Acid Compound Synthesis Example C

1,300 grams of food grade canola oil and 2.9 grams of Engelhard “N-545”nickel hydrogenation catalyst are placed in a hydrogenation reactorwhich is equipped with a stirrer. The reactor is sealed and evacuated.The contents are heated to 180° C. and hydrogen is fed into the reactor.Stirring is maintained at 450 rpm throughout the course of the reaction.After 5minutes the temperature in the reactor is 192° C. and thehydrogen pressure is 10 psig. The temperature is held at 190±3° C. After105 minutes from the start of the hydrogen feed, the hydrogen pressureis 10 psig. A sample of the reaction mass is drawn and found to have anIodine Value of 85.5. After another 20 minutes at 190° C., the hydrogenpressure is 10 psig. The hydrogen feed is discontinued and the reactorcontents cooled with stirring. The final reaction product has an IodineValue of 82.4. The product that forms in the reactor is removed andfiltered. It has a cloud point of 17.2° C.

Fatty Acid Compound Synthesis Example D

1,300 grams of food grade canola oil and 1.4 grams of Engelhard “N-545”®nickel hydrogenation catalyst are placed in a hydrogenation reactorwhich is equipped with a stirrer. The reactor is sealed and evacuated.The contents are heated to 180° C. and hydrogen is fed into the reactor.After 5 minutes the temperature in the reactor is 191° C. and thehydrogen pressure is 10 psig. The temperature is held at 190±3° C. After100 minutes from the start of the hydrogen feed, the hydrogen pressureis 10 psig. A sample of the reaction mass is drawn and found to have anIodine Value of 95.4. After another 20 minutes at 190° C., the hydrogenpressure is 10 psig. The hydrogen feed is discontinued and the reactorcontents cooled with stirring. The final reaction product had an IodineValue of 2.3. The product that forms in the reactor is removed andfiltered. It has a cloud point of 34° C.

Fatty Acid Compound Synthesis Example E

1,300 grams of food grade canola oil and 1.3 grams of Engelhard “N-545”® nickel hydrogenation catalyst are placed in a hydrogenation reactorwhich is equipped with a stirrer. The reactor is sealed and evacuated.The contents are heated to 190° C. and hydrogen is fed into the reactorto a hydrogen pressure of 5 psig. After 3 hours from the start of thehydrogen feed, a sample of the reaction mass is drawn and found to havean iodine value of 98. The hydrogenation is interrupted, another 0.7grams of the same catalyst is added, and the reaction conditions arereestablished at 190° C. for another 1 hour. The hydrogen feed is thendiscontinued and the reactor contents cooled with stirring. The finalreaction product had an Iodine Value of 89.9. The product that forms inthe reactor is removed and filtered. It has a cloud point of 16.0° C.

Fatty Acid Compound Synthesis Example F

1,300 grams of food grade canola oil and 2.0 grams of Engelhard “N-545”®nickel hydrogenation catalyst are placed in a hydrogenation reactorwhich is equipped with a stirrer. The reactor is sealed and evacuated.The contents are heated to 190° C. and hydrogen is fed into the reactorto a hydrogen pressure of 5 psig. Stirring is maintained at 420 rpmthroughout the course of reaction of the hydrogen feed. After 130minutes from the start of the hydrogen feed, the hydrogen feed isdiscontinued and the reactor contents cooled with stirring. The finalreaction product had an Iodine Value of 96.4. The product that forms inthe reactor is removed and filtered. It has a cloud point of 11.2° C.

Fatty acid Compound Synthesis Example G

A mixture of 1,200 grams of the hydrogenated oil from Synthesis ExampleF and 200 grams of the hydrogenated oil from Synthesis Example A ishydrolyzed three times with 250° C. steam at 600 psig for 2.5 hours at aratio of steam:oil of 1.2 (by weight). An aqueous solution containingthe glycerine which had split off is removed.

The resulting mixture of fatty acids is vacuum distilled for a total of150 minutes, in which the pot temperature rose gradually from 200° C. to238° C. and the head temperature rose gradually from 175° C. to 197° C.Vacuum of 0.3-0.6 mm is maintained.

The fatty acids product of the vacuum distillation has an Iodine Valueof 99.1, an amine value (AV) of 197.6 and a saponification value (SAP)of 198.6.

The following are synthesis examples of softener compounds aacording tothe present invention:

Synthesis Example of Softener Compound 1

1)-Esterification:

489 grams of partly hydrogenated tallow fatty acid with an IV of 45 andan Acid Value of 206, commercially available under the tradename Distal51 and sold by Witco Corporation, is added into the reactor, the reactoris flushed with N2 and 149 grams of triethanolamine is added underagitation. The molar ratio of fatty acid to triethanol amine is of1.8:1. The mixture is heated above 150 C and the pressure is reduced toremove the water of condensation. The reaction is prolonged until anAcid Value of 5 is reached.

The above mentioned partly hydrogenated tallow fatty acid is alsocommercially available from Henkel under the tradename Edenor HtiCT, orcommercially available from Unichema under the tradename Prifac 5905.

2)-Quaternization:

To 627 grams of the product of condensation, 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50° C. and the reaction is followed by verifyingthe residual amine value. 749 grams of softener compound of theinvention is obtained.

The quaternized material is optionally diluted with e.g. 15% ofisopropanol which lower the melting point of the material therebyproviding a better ease in the handling of the material.

Synthesis Example of Softener Compound 2

1)-Esterification:

504 grams of oleic fatty acid with an IV of 90 and an Acid Value of 198,commercially available under the tradename Emersol 233 and sold byHenkel Corporation, is added into the reactor, the reactor is flushedwith N2 and 149 grams of triethanolamine is added under agitation. Themolar ratio of fatty acid to triethanol amine is of 1.8:1. The mixtureis heated above 150 C and the pressure is reduced to remove the water ofcondensation. The reaction is prolonged until an Acid Value of 2 isreached.

The above mentioned oleic fatty acid is also commercially available fromHenkel under the tradename Edenor TiO5.

2)-Quaternization:

To the 629 grams of the product of condensation 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50 C and the reaction is followed by verifying theresidual amine value.

751 grams of softener compound of the invention is obtained.

The quaternized material is optionally diluted with e.g. 8% of ethanolwhich lower the melting point of the material thereby providing a betterease in the handling of the material.

Synthesis Example of softener compound 3

1-Esterification:

571 grams of Canola fatty acid with an IV of about 100 and an Acid Valueof about 196 as made according to Fatty Acid Compound Synthesis ExampleG is added into the reactor, the reactor is flushed with N2 and 149grams of triethanolamine is added under agitation. The molar ratio offatty acid to triethanol amine is of 2.0:1. The mixture is heated above150 C and the pressure is reduced to remove the water of condensation.The reaction is prolonged until an Acid Value of 3 is reached.

2)-Quaternization:

To the 698 grammes of the product of condensation 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50 C and the reaction is followed by verifying theresidual amine value.

820 grams of softener compound of the invention is obtained.

The quaternized material is optionally diluted with e.g. 15% of a 50:50ethanol/hexyleneglycol mixture which lower the melting point of thematerial thereby providing a better ease in the handling of thematerial.

Synthesis Example of Softener Compound 4

1)-Esterification:

457 grams of Canola fatty acid with an IV of about 100 and an Acid Valueof about 196, as made according to Fatty Acid Compound Synthesis ExampleG, is added into the reactor, the reactor is flushed with N2 and 149grams of triethanolamine is added under agitation. The molar ratio offatty acid to triethanol amine is of 1.6:1. The mixture is heated above150 C and the pressure is reduced to remove the water of condensation.The reaction is prolonged until an Acid Value of 1 is reached.

2)-Quaternization:

To the 582 grams of the product of condensation 122 grams ofdimethylsulfate is added under continuous agitation. The reactionmixture is kept above 50 C and the reaction is followed by verifying theresidual amine value.

704 grams of softener compound of the invention is obtained.

The quaternized material is optionally diluted with e.g. 8% of ethanolwhich lower the melting point of the material thereby providing a betterease in the handling of the material.

The above synthesised softener compound are also exemplified below inthe non-limiting fabric softening composition examples.

Abbreviations used in the Examples

In the softening compositions, the abreviated component identificationhave the following meanings:

Softener compound 1: Softener compound as made according to SynthesisExample of softener compound 1

Softener compound 2: Softener compound as made according to SynthesisExample of softener compound 2

Softener compound 3: Softener compound as made according to SynthesisExample of softener compound 3

Softener compound 4: Softener compound as made according to SynthesisExample of softener compound 4

IPA: Isopropylalcohol

TMPD: 2,2,4-trimethyl-1,3-pentanediol

CHDM: 1,4 cyclohexanedimethanol

1 2 3 4 5 Softener 8.0 — — — — compound 1 Softener — 8.0 20 30 28compound 2 IPA 1.4 — — — — Ethanol — 0.7 1.7 2.6 2.4 1,2 Hexanediol — 1015 — — 2-ethyl-1,3- — — — — 12 hexanediol TMPD — — — 12 — CHDM — — — 5 5HCl 0.02 0.02 0.02 0.02 0.02 Calcium 0.04 — — — — chloride Perfume 0.50.5 1.0 2.0 2.0 Dye 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm Deminerised BalanceBalance Balance Balance Balance water 6 7 8 9 Softener 8.0 25 — 28compound 3 Softener — — 30 — compound 4 Ethanol 0.7 2.2 2.6 2.5 Hexyleneglycol 0.7 2.2 — 2.5 1,2 Hexanediol 9 12 15 5 TMPD — 5 — 9 HCl 0.02 0.020.02 0.02 Perfume 0.5 1.5 1.0 2.0 Dye 5 ppm 20 ppm 20 ppm 5 ppm Deminwater Balance Balance Balance Balance

What is claimed is:
 1. A clear liquid fabric softening compositioncomprising a) a biodegradable fabric softener compound, wherein thesoftener compound comprises a quaternary ammonium salt, the quaternisedammonium salt being a quaternised product of a condensation productbetween: i) a fraction of saturated or unsaturated, linear or branchedfatty acids, or of derivatives of said acids, said fatty acids orderivatives each possessing a hydrocarbon chain in which the number ofatoms is between 5 and 21, and ii) triethanolamine, characterized inthat said condensation product has an acid value measured by titrationof the condensation product with a standard solution against aphenolphthalein indicator, of less than 6.5 and wherein the mole ratioof i) to ii) is from 1.8:1 to 2.2:1; b) water; and c) principal solventin an amount effective to provide a clear composition.
 2. A clear liquidfabric softening composition according to claim 1, wherein the fattyacid/triethanolamine mole ratio is 2.0:1.
 3. A clear liquid fabricsoftening composition according to claim 1, wherein the biodegradablefabric softener compound has an acid value of less than
 5. 4. A clearliquid fabric softening composition according to claim 1, wherein thebiodegradable fabric softener compound has an acid value of less than 3.5. A clear liquid fabric softening composition according to claim 1,wherein the biodegradable fabric softener compound has the formula:[(R)_(4−m)—N⁽⁺⁾—[(CH₂)_(n)—Y—R¹]_(m)]X⁽⁻⁾ wherein each R substituent ishydrogen or a short chain C₁-C₆ alkyl or hydroxyalkyl group; each m is 2or 3; n is 2; each Y is —O—(O)C—, —(R)N—(O)C—, —C(O)—N(R)—, or —C(O)—O—;the sum of carbons in each R¹, plus one when Y is —O—(O)C— or—(R)N—(O)C—, is C₆-C₂₂, but no more than one R¹, or YR¹, sum being lessthan 12 and then the other R¹, or YR¹, sum is at least 16, with each R¹comprising a long chain C₅-C₂₁ branched alkyl or unsaturated alkyl,optionally substituted, the ratio of branched alkyl to unsaturated alkylbeing from 5:95 to 95:5, and for the unsaturated alkyl group, the IodineValue of the parent fatty acid of this R¹ group is from 20 to 140, andwherein the counterion, X⁻ is a softener-compatible anion.
 6. Abiodegradable fabric softener compound according to claim 1, wherein thefatty acid fraction contains cis and trans isomers with a cis/transratio of from 1:1 to 50:1.
 7. A clear liquid fabric softeningcomposition according to claim 1, wherein the principal solvent isselected from mon-ols, C6 diols, C7 diols, octanediol isomers,butanediol derivatives, trimethylpentanediol isomers,ethylmethylpentanediol isomers, propyl pentanediol isomers,dimethylhexanediol isomers, ethylhexanediol isomers, methylheptanediolisomers, octanediol isomers, nonanediol isomers, alkyl glyceryl ethers,di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic glycerylethers, alicyclic diols and derivatives, C₃C₇ diol alkloxylatedderivatives, aromatic diols, and unsaturated diols, and mixturesthereof.
 8. A clear liquid fabric softening composition according toclaim 1, wherein the mole ratio of i) to ii) is from 2.0:1 to 2.2:1. 9.A clear liquid fabric softening composition comprising a) abiodegradable fabric softener compound, the softener compound comprisinga quaternary ammonium salt, the quaternised ammonium salt being aquaternised product of a condensation product between: i) a fraction ofsaturated or unsaturated, linear or branched fatty acids, or ofderivatives of said acids, said fatty acids or derivatives eachpossessing a hydrocarbon chain in which the number of atoms is between 5and 21, and ii) triethanolamine, characterized in that said condensationproduct has an acid value measured by titration of the condensationproduct with a standard solution against a phenolphthalein indicator, ofless than 6.5, said biodegradable fabric softener compound is present inan amount of from 1% to 80%, by weight of the composition; and b) aprincipal solvent having a ClogP of from 0.15 to 0.64 in an amount from6% to less than 40% by weight of the composition and effective toprovide a clear composition.
 10. A fabric softening compositionaccording to claim 9, wherein said principal solvent is selected frommonols, C6 diols, C7 diols, butanediol derivatives, trimethylpentanediolisomers, ethylmethylpentanediol isomers, propyl pentanediol isomers,dimethylhexanediol isomers, ethylhexanediol isomers, methylheptanediolisomers, octanediol isomers, nonanediol isomers, alkyl glyceryl ethers,di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic glycerylethers, alicyclic diols and derivatives, C₃-C₇ diol alkloxylatedderivatives, aromatic diols, and unsaturated diols, and mixturesthereof.
 11. A fabric softening composition according to claim 10,wherein the principal solvent is selected from2,2,4-trimethyl-1,3-pentanediol, ethoxylates of2,2,4-trimethyl-1,3-pentanediol, 1,2 hexanediol, ethoxylates of2-ethyl-1,3-hexanediol, 1,2 cyclohexanedimethanol, and mixtures thereof.12. A fabric softening composition according to claim 11, wherein saidprincipal solvent is present in a combination form of2,2,4-trimethyl-1,3-pentanediol and 1,2 hexanediol.
 13. A fabricsoftening composition according to claim 9, wherein said compositioncomprises an effective amount, sufficient to improve clarity, of lowmolecular weight water soluble solvents selected from the groupconsisting of: ethanol, isopropanol, propylene glycol, 1,3-propanediol,propylene carbonate, 1,4 cyclohexanedimethanol and mixtures thereof,said water soluble solvents being at a level that will not form clearcompositions by themselves.
 14. A premix composition comprising a) afabric softener compound comprising a quaternary ammonium salt, thequaternised ammonium salt being a quaternised product of a condensationproduct between: i) a fraction of saturated or unsaturated, linear orbranched fatty acids, or of derivatives of said acids, said fatty acidsor derivatives each possessing a hydrocarbon chain in which the numberof atoms is between 5 and 21, and ii) triethanolamine, characterized inthat said condensation product has an acid value measured by titrationof the condensation product with a standard solution against aphenolphthalein indicator, of less than 6.5; and b) at least onecomponent selected from the group consisting of principal solvents, lowmolecular weight water soluble solvents, water soluble calcium salt,water soluble magnesium salt, perfume and mixtures thereof, the premixhaving a viscosity of less than 1,000 cps.
 15. A clear fabric softeningcomposition comprising a) a biodegradable fabric softening compoundcomprising a quaternary ammonium salt, the quaternary ammonium saltbeing a quaternised product of a condensation product between: i) afraction of saturated or unsaturated, linear or branched fatty acids, orof derivatives of said acids, said fatty acids or derivatives eachpossessing a hydrocarbon chain in which the number of atoms is between 5and 21, and ii) alkanolamine having alkanol groups of 1 to 4 carbonatoms, characterized in that said condensation product has an acid valuemeasured by titration of the condensation product with a standardsolution against a phenolphthalein indicator, of less than 6.5 andwherein the mole ratio of i) to ii) is from 1.8:1 to 2.2:1, the compoundhaving the formula: [(R)_(4−m)—N⁽⁺⁾—[(CH₂)_(n)—Y—R¹]_(m])X⁽⁻⁾ whereineach R substituent is hydrogen or a short chain C₁-C₆ alkyl orhydroxyalkyl group; each m is 2 or 3; each n is from 1 to 4; each Y is—O—(O)C—, —(R)N—(O)C—, —C(O)—N(R)—, or —C(O)—O—; the sum of carbons ineach R¹, plus one when Y is —O—(O)C— or —(R)N—(O)C—, is C₆-C₂₂, but notmore than one R¹, or YR¹, sum being less than 12 and then the other R¹,or YR¹, sum is at least 16, with each R¹ comprising a long chain C₅-C₂₁branched alkyl or unsaturated alkyl, optionally substituted, the ratioof branched alkyl to unsaturated alkyl being from 5:95 to 95:5, and forthe unsaturated alkyl group, the Iodine Value of the parent fatty acidof this R¹ group is from 20 to 140, and wherein the counterion, X— is asoftener-compatible anion; b) water; and c) principal solvent, in anamount effective to provide a clear composition.